Influence of cultivar and technological conditions on the volatile profile of virgin pistachio oils.

The main aim of this work was to characterize the volatile profile of virgin pistachio oils produced from eight cultivars (Aegina, Avdat, Kastel, Kerman, Larnaka, Mateur, Napoletana and Sirora), under different technological conditions (temperature, roasting, use of whole nuts, screw speed and nozzle diameter), and compare it with those of commercial pistachio oils. Terpenes (15.57-41.05 mg/kg), accounting for ~97% of total volatiles, were associated with appreciated sensory properties, with α-pinene as the main volatile (14.47-37.09 mg/kg). Other terpene compounds such as limonene (0.11-3.58 mg/kg), terpinolene (0.00-1.61 mg/kg), ß-pinene (0.12-1.20 mg/kg) and α-terpineol (0.00-1.17 mg/kg) were quantified at lower concentrations. Acids, alcohols, aldehydes, esters and hydrocarbons only summed to ~3% of the total volatile compounds. The volatiles content greatly depended on the pistachio cultivar employed. The influence of extraction conditions was also very relevant; in particular, terpenes doubled (28.38-53.84 mg/kg) using whole pistachios for oil extraction, also being incremented by mild processing conditions. On the contrary, higher temperature or roasting decreased the terpene content (~50-25% respectively), and pyrazines appeared (up to 3.12 mg/kg).

Development of functional edible oils enriched with pistachio and walnut phenolic extracts.

The purpose of this research was the development of functional edible oils with potential health promoting effects, enriched with phenolic-rich extracts obtained from pistachio and walnut. A high phenolic content, 10860 mg/kg and 7030 mg/kg in walnut and pistachio kernels respectively, with a corresponding strong radical scavenging effect (DPPH, 106 and 20 mmol/kg Trolox) were found. The remarkable antioxidant capacity of the phenolic-rich extracts prepared form walnut (255 mol/kg Trolox, measured by DPPH, 1500 times higher than its kernel) and pistachio (13 mol/kg, 630 times higher) makes them good candidates to evaluate their potential as bioactive ingredients. In the different enriched edible oils studied, a phenolic concentration of 340-570 mg/kg has been reached, showing the functional oils a great antioxidant activity, which was apparently much higher when walnut extracts were employed (e.g. 54 mmol/kg Trolox, as DPPH).

Functional and sensory properties of pistachio nuts as affected by cultivar.

BACKGROUND: Modern agriculture allows farmers to choose among different cultivars of the same fruit to fulfill their agronomic needs and consumers' demands; however, there are only a few studies that describe and compare key functional and sensory properties of different pistachio cultivars. The main objective of this study was to compare eight pistachio cultivars by analyzing key functional properties (phenolic compounds, polymeric procyanidins, antioxidant activity, and inhibition of α-amylase and ß-glucosidase), aromatic compounds with gas chromatography-mass spectrometry (GC-MS), and by examining their sensory properties with a trained panel. RESULTS: A combination of LC-PDA-MS-QTof (liquid chromatography photodiode array quadrupole time-off flight mass spectrometry) and electrospray ionization was used to determine two phenolic acids, nine flavonols, one anthocyanin, and three flavan-3-ols in pistachio cultivars, with a total concentration ranging from 500 to 6065 mg 100 g-1 dry weight (dw). The total polymeric procyanidins concentrations oscillated between 348 and 5919 mg 100 g-1 dw, (-)-epicatechin being the major monomer contributor. Pinene was the most abundant volatile compound (∼200 mg kg-1 dw), and, in the sensory analysis of samples, 23 sensory attributes were found to differ significantly among the cultivars. CONCLUSION: The cultivar 'Larnaka' stood out as having the best functional profile (high polyphenolic content, high antioxidant activity, and high values of α-amylase and ß-glucosidase inhibition), and the cultivars 'Kastel' and 'Kerman' showed the most attractive sensory properties, mainly the most intense flavor. © 2019 Society of Chemical Industry.

Comprehensive Study of the Phenolic Compound Profile and Antioxidant Activity of Eight Pistachio Cultivars and Their Residual Cakes and Virgin Oils.

Phenolic compounds of eight pistachio ( Pistacia vera L.) cultivars and their residual cakes and virgin oils (screw pressing) were studied using high-performance liquid chromatography-diode array detection-electrospray ionization-tandem mass spectrometry. A total of 25 compounds were identified and quantified for pistachio nuts and residual cakes, with the presence of five flavonols, six flavanols, and one gallotannin being reported for the first time. Total phenolics in pistachio nuts showed a concentration from 1359 mg/kg (Kastel) to 4507 mg/kg (Larnaka). Flavanols were the most abundant phenolics, at about 90%, with resulting procyanidin B1 and gallocatechin being the main phenolics, depending upon the cultivar. Other phenolic groups, such as anthocyanins (from 54 to 218 mg/kg), flavonols (from 76 to 130 mg/kg), flavanones (from 12 to 71 mg/kg), and gallotannins (from 4 to 46 mg/kg), were also identified. Residual cakes presented the same phenolic profile but with a concentration almost double because of the concentration effect caused by the oil separation. Virgin pistachio oils showed a very low phenolic content, with eriodyctiol being the only compound identified.

Characterization of virgin walnut oils and their residual cakes produced from different varieties.

This study addresses the composition and properties of different walnut varieties (Chandler, Hartley and Lara), in particular their virgin oils and residual cakes obtained by screw pressing employing different cultivars. Among nuts, walnut (Juglans regia L.) exhibits interesting nutritional value, mainly due to their high content in linoleic acid, phenolic and tocopherol compounds, which show antioxidant and other healthy properties. Valuable results related to fatty acid profile and minor components were observed. Virgin walnut oil is a rich source in linoleic acid (60-62%) and γ-tocopherol (517-554 mg/kg). Moreover, walnuts show a very high content in total phenolic compounds (10,045-12,474 mg/kg; as gallic acid), which contribute to a great antioxidant activity (105-170 mmol/kg for DPPH, and 260-393 mmol/kg for ORAC), being the hydrolysable tannins (2132-4204 mg/kg) and flavanols (796-2433 mg/kg) their main phenolic groups. Aldehydes account for the highest contribution to aromatic volatiles in virgin walnut oil (about 35% of total). As expected, polar phenolic compounds concentrate in the residual cake, after the separation of the oily phase, reaching a content of up to 19,869 mg/kg, leading to potential added value and applications as source of bioactive compounds to this by-product.

Composition and properties of virgin pistachio oils and their by-products from different cultivars.

Pistachios (Pistacia vera) exhibit an interesting nutritional value, due to the high content of oleic acid and minor components with antioxidant and bioactive properties. This work aimed to characterize pistachio virgin oils and their partially defatted residual cakes, obtained from eight cultivars (Aegina, Avdat, Kastel, Kerman, Larnaka, Mateur, Napoletana, and Sirora). Interesting results on phenolics, tocopherols and antioxidant activity were observed, which were greatly affected by variety. Pistachio virgin oils are rich in healthy oleic acid (55-74%), phytosterols (3200-7600mg/kg) and γ-tocopherol (550-720mg/kg). A high content of phenolic compounds (8600-15000mg/kg gallic acid equivalents) and the corresponding antioxidant activities (12-46 and 155-496mmol/kg for DPPH and ORAC) of the residual cakes demonstrate their potential applications as functional ingredients and as rich sources of bioactive compounds. Moreover, virgin pistachio oils possess peculiar and pleasant sensory characteristics, contributing greater added value to the consumers compared to refined vegetable oils.

Stability of Virgin Olive Oil Phenolic Compounds during Long-Term Storage (18 Months) at Temperatures of 5-50 °C.

Virgin olive oil (VOO) phenolic compounds have high nutritional and biological properties. The purpose of this research was to study the stability of VOO phenolic compounds during long-term storage (18 months) at different temperatures (5, 15, 25, and 50 °C) and to verify the advantage of storing VOO at a temperature lower than the usual commercial conditions (20-25 °C). Four monovarietal VOOs that differed in their fatty acid profile and content of natural antioxidants were used in this study. The degradation of secoiridoid phenolics during storage displayed pseudo-first-order kinetics and depended on the initial content of phenolics related to olive oil variety. The initial degradation rate was similar at 5 and 15 °C but increased considerably at 25 °C and was even faster at 50 °C. Tyrosol derivatives were more stable than hydroxytyrosol compounds, especially in closed bottles with limited oxygen availability. The increase in the content of simple phenolics, the decrease of their secoiridoid derivatives, or the ratio of simple to secoiridoid phenolics could be used as indices of the oxidative and hydrolytic degradation of VOO phenolics. The shelf life of the studied VOO was considerably extended at reduced storage temperature (15 vs 25 °C). Moreover, storage conditions affected VOO phenolic content and therefore the expiration date of the health claim that olive oil polyphenols contribute to the protection of blood lipids from oxidative stress.

Antioxidant capacity of individual and combined virgin olive oil minor compounds evaluated at mild temperature (25 and 40°C) as compared to accelerated and antiradical assays.

The individual and combined antioxidant and antiradical capacity of the main minor compounds of virgin olive oil (α-tocopherol, hydroxytyrosol, tyrosol and oleuropein aglycone) spiked in Purified Olive Oil (POO) as the lipid matrix model is described. The antioxidant activity was assessed under mild temperature conditions (25 and 40°C) to mimic the autoxidation process during real storage conditions. These results were compared with accelerated (Rancimat Induction Period) and antiradical (DPPH) tests. The higher concentration of o-diphenols (hydroxytyrosol or oleuropein aglycone) in olive oil led to a lower oxidation rate under the conditions studied, resulting in a strong antioxidant effect. Remarkably α-tocopherol acted as a pro-oxidant at 25 and 40°C, in particular during the first oxidation stage. In contrast, this compound behaved as an antioxidant under Rancimat and DPPH conditions. The oxidation rate constant as a function of the concentration of spiked compound fit an exponential decay model very well and therefore the progress of the oxidation reaction could be predicted. No synergistic or antagonistic effects were generally observed when combined antioxidant compounds were assayed.

Effect of preprocessing olive storage conditions on virgin olive oil quality and composition.

The quality of virgin olive oil (VOO) is intimately related to the characteristics and composition of the olive fruit at the moment of its milling. In this study, the determination of suitable olive storage conditions and feasibility of using this preprocessing operation to modulate the sensory taste of VOO are reported. Several olive batches were stored in different conditions (from monolayer up to 60 cm thickness, at 20 and 10 degrees C) for a period of up to three weeks, and the quality and composition of minor constituents, mainly phenols and volatiles, in the corresponding VOO were monitored. Cornicabra cultivar VOO obtained from drupes stored for 5 or 8 days at 20 or 10 degrees C, respectively, retained the "extra virgin" category, according to chemical quality indices, since only small increases in free acidity and peroxide values were observed, and the bitter index of this monovarietal oil was reduced by 30-40%. Storage under monolayer conditions at 10 degrees C for up to two weeks is also feasible because "off-odor" development was delayed, a 50% reduction in bitterness was obtained, and the overall good quality of the final product was preserved.

Effect of malaxation conditions on phenol and volatile profiles in olive paste and the corresponding virgin olive oils (Olea europaea L. Cv. Cornicabra).

Malaxation of olive paste must be considered to be much more than a simple physical separation, because a complex bioprocess takes place that is very relevant to the quality and composition of the final product. A combined study of the effect of kneading temperature and time on the minor composition of olive paste and its corresponding virgin olive oil, processed in an experimental oil mill (Pieralisi, Fattoria) with a working capacity of 200 kg/h, is reported. A large drop in the oleuropein content in the olive paste with respect to its initial content in the olive fruit (between 92 and 96%) was observed, which suggested its almost total degradation during the crushing operation. The major phenolic compound found in the olive paste during kneading was the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA, always higher than 60% of the total phenols). This greatly decreased during malaxation (from 5505 to 2317 mg/kg, on average). The content of phenolic compounds in virgin olive oil was much more affected by the malaxation temperature than the kneading time. For instance, the 3,4-DHPEA-EDA content increased by 220-630% in the two batches when the temperature was increased from 20 to 40 degrees C. A reduction in the C6 aldehydes was found in virgin olive oil as the malaxation temperature increased, especially in E-2-hexenal (30% reduction). In contrast, C6 aldehydes in the oils from the oil mill plant significantly increased as the malaxation time increased from 30 to 90 min, chiefly E-2-hexenal (about a 70% increase).

Comparative study of virgin olive oil behavior under Rancimat accelerated oxidation conditions and long-term room temperature storage.

Oxidative stability should be one of the most important quality markers of edible oils; nevertheless, it is not recognized as a legal parameter. The results reported in this study highlight the differences in the olive oil oxidation process under Rancimat accelerated conditions with respect to long-term storage at room temperature and clearly show the lack of correlation between shelf life and the Rancimat induction period. A better correlation, although not yet satisfactory, was found when the same oxidation end-point was used in both assays. The parameter K 270, a marker of secondary oxidation products, was the first index to reach the established upper legal limit under Rancimat conditions, whereas at 25 degrees C it was an index of primary oxidation products ( K 232). Furthermore, the ratio of oxidation rate at Rancimat conditions to oxidation rate at 25 degrees C was more than double for secondary oxidation products compared with primary ones. Notable differences were also observed in degradation rates of the different unsaturated fatty acids and in rates of formation of polar oxidation compounds. Moreover, under the Rancimat conditions antioxidants such as o-diphenols and alpha-tocopherol rapidly depleted, and when they had practically disappeared, there was a sharp increase in oxidation indices, such as peroxide value, and in oxidation products. At 25 degrees C, on the other hand, the depletion was much lower.

Retention effects of oxidized polyphenols during analytical extraction of phenolic compounds of virgin olive oil.

The hydrophilic extract of virgin olive oil contains several phenolic compounds such as simple phenols, lignans, and secoiridoids that have been widely studied in recent years. Interest in the hydrophilic extract has also been extended to the fraction of oxidized phenols that form during storage as a consequence of oxidative stress. The present investigation compares the two most commonly used extraction methods, namely liquid-liquid extraction and SPE, on fresh virgin olive oil and that kept at different temperatures in the presence of oxygen to promote the formation of oxidative products. The selective retention of these natural and oxidized phenolic compounds in relation to the extraction method was assessed. Quantification of eight identified phenolic molecules and 11 unknown peaks was performed by HPLC-DAD/MSD.

Phenolic and volatile compounds of extra virgin olive oil (Olea europaea L. Cv. Cornicabra) with regard to fruit ripening and irrigation management.

This study investigated the effect of both the degree of ripening of the olive fruit and irrigation management-rain-fed, two different regulated deficit irrigations (RDI), the method proposed by the Food and Agriculture Organization of the United Nations (known as FAO), and 125 FAO (125% FAO)-on the phenolic and volatile composition of Cornicabra virgin olive oils obtained during two crop seasons. Secoiridoid phenolic derivatives greatly decreased upon increase of both irrigation and ripening, for example, the 3,4-DHPEA-EDA content decreased from 770 to 450 mg/kg through fruit ripening under rain-fed conditions and from 676 to 388 mg/kg from rain-fed conditions to FAO irrigation treatment (at a ripeness index of approximately 4). Moreover, secoiridoid derivatives of hydroxytyrosol decreased more than those of tyrosol. The levels of major volatile components decreased in the course of ripening but were higher in irrigated olive oils: for example, the E-2-hexenal content ranged between 4.2 and 2.6 mg/kg (expressed as 4-methyl-2-pentanol) over fruit maturation under rain-fed conditions and between 8.0 and 3.5 mg/kg under FAO scheduling. It is important to note that where water was applied only from the beginning of August (RDI-2), when oil begins to accumulate in the fruit, the resulting virgin olive oil presented a phenol and volatile profile similar to those of the FAO and 125 FAO methods, but with a considerable reduction in the amount of water supplied to the olive orchard.

Effect of storage on secoiridoid and tocopherol contents and antioxidant activity of monovarietal extra virgin olive oils.

The degradation of secoiridoid, tocopherol, and antioxidant activity in extra virgin olive oils (EVOOs) was studied during 8 months of storage in closed bottles in the dark, at 40 and 25 degrees C. Picual, Arbequina, Taggiasca, and Colombaia monovarietal EVOOs possessing quite different fatty acid and antioxidant contents were used. The secoiridoid aglycones, namely, the oleuropein and ligstroside derivatives, and alpha-tocopherol decreased following pseudo-first-order kinetics. In all EVOOs oleuropein derivatives were less stable than the corresponding ligstroside derivatives and alpha-tocopherol. Accordingly, overall antioxidant activity decreased following pseudo-first-order kinetics, with rate constants ranging from 0.85 x 10(-)(3) to 4.1 x 10(-)(3) days(-)(1) at 40 degrees C and from 0.8 x 10(-)(3) to 1.5 x 10(-)(3) days(-)(1) at 25 degrees C. According to both the antioxidant activity and the hydrolysis and oxidation indices established by EU regulation to assess EVOO quality, Colombaia oil was the least stable, followed by Taggiasca, Arbequina, and Picual oils. Despite antioxidant degradation, EVOOs with high antioxidant contents were still "excellent" after 240 days of storage at 40 degrees C. These data led to the conclusion that the beneficial properties of EVOOs due to antioxidant activity can be maintained throughout their commercial lives.

Changes in phenolic composition and antioxidant activity of virgin olive oil during frying.

The concentration of hydroxytyrosol (3,4-DHPEA) and its secoiridoid derivatives (3,4-DHPEA-EDA and 3,4-DHPEA-EA) in virgin olive oil decreased rapidly when the oil was repeatedly used for preparing french fries in deep-fat frying operations. At the end of the first frying process (10 min at 180 degrees C), the concentration of the dihydroxyphenol components was reduced to 50-60% of the original value, and after six frying operations only about 10% of the initial components remained. However, tyrosol (p-HPEA) and its derivatives (p-HPEA-EDA and p-HPEA-EA) in the oil were much more stable during 12 frying operations. The reduction in their original concentration was much smaller than that for hydroxytyrosol and its derivatives and showed a roughly linear relationship with the number of frying operations. The antioxidant activity of the phenolic extract measured using the DPPH test rapidly diminished during the first six frying processes, from a total antioxidant activity higher than 740 micromol of Trolox/kg down to less than 250 micromol/kg. On the other hand, the concentration of polar compounds, oxidized triacylglycerol monomers (oxTGs), dimeric TGs, and polymerized TGs rapidly increased from the sixth frying operation onward, when the antioxidant activity of the phenolic extract was very low, and as a consequence the oil was much more susceptible to oxidation. The loss of antioxidant activity in the phenolic fraction due to deep-fat frying was confirmed by the storage oil and oil-in-water emulsions containing added extracts from olive oil used for 12 frying operations.

Phenolic compounds profile of cornicabra virgin olive oil.

This study presents the phenolic compounds profile of commercial Cornicabra virgin olive oils from five successive crop seasons (1995/1996 to 1999/2000; n = 97), determined by solid phase extraction reversed phase high-performance liquid chromatography (SPE RP-HPLC), and its relationship with oxidative stability, processing conditions, and a preliminary study on variety classification. The median of total phenols content was 38 ppm (as syringic acid), although a wide range was observed, from 11 to 76 ppm. The main phenols found were the dialdehydic form of elenolic acid linked to tyrosol (p-HPEA-EDA; 9 +/- 7 ppm, as median and interquartile range), oleuropein aglycon (8 +/- 6 ppm), and the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA; 5 +/- 8 ppm). In many cases the correlation with oxidative stability was higher when the sum of the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA) and oleuropein aglycon (r (2) = 0.91-0.96) or the sum of these two and hydroxytyrosol (r (2) = 0.90-0.97) was considered than was observed with HPLC total phenols (r (2)= 0.91-0.95) and especially with colorimetric determination of total polyphenols and o-diphenols (r (2) = 0.77-0.95 and 0.78-0.92, respectively). 3,4-DHPEA-EDA, p-HPEA-EDA, the aglycons of oleuropein and ligstroside, and HPLC total phenols content presented highly significant differences (p = 0.001-0.010) with respect to the dual- and triple-phase extraction systems used, whereas colorimetric total polyphenols content did not (p = 0.348) and o-diphenols showed a much lower significant difference (p = 0.031). The five variables that most satisfactorily classified the principal commercial Spanish virgin olive oil varieties were 1-acetoxypinoresinol, 4-(acetoxyethyl)-1,2-dihydroxybenzene (3,4-DHPEA-AC), ligstroside aglycon, p-HPEA-EDA, and RT 43.3 contents.